Azodyestuffs



Patented Feb. 4, 1936 UNITED STATES PATENT OFFICE AZODYESTUFFS Jos Stephen Petrus-Blumberger, Delft, Netherlands, assignor to General Aniline Works, Inc., New York, N. Y., a. corporation of Delaware No Drawing. Application April 12, 1932, Serial No. 604,881. In Germany April 20, 1931 6 Claims.

The present invention relates to new azodyestuffs, more particularly it relates to dyestuffs which may be represented by the probable genwherein R stands for a radical of the benzene or naphthalene series containing a sulfonic or a carboxylic acid group, one X stands for hydrogen and the other X stands for hydrogen or a sulfonic acid group, R stands for alkyl, such as methyl, ethyl, hydroxyethyl, propyl, isopropyl, n stands for the numbers one or two, and wherein the benzene nucleus R" may be substituted by halogen, alkyl or alkoxy.

My new dyestufis are obtainable by diazotizing in the usual manner a primary amine of the benzene or naphthalene series containing a sulfonic or a carboxylic acid group and coupling with an l-amino-2-naphtholalkylether or a 6- or 7-sulfonic acid thereof, further diazotizing and coupling with an l-(aminobenzoylamino) B-naphthol-monoor disulfonic acid which may be substituted in the benzene nucleus of the benzoylamino group by alkyl, alkoxy or halogen, thereby effecting the final coupling with the addition of a base of the pyridine or quinoline series, such as picoline, quinaldine and preferably pyridine itself.

As initial components there may be mentioned by way of example, aminobenzoic acid, anilinesulfonic acid, 1-naphthylamine-4-sulfonic acid, 2-naphthylamine-8-sulfonic acid, p-toluidine-msulfonic acid, chloro-toluidine sulfonic acids, 2- anisidine-i-sulfonic acid (OCH3=1) m-xylidinem-sulfonic acid.

As final coupling components there may be mentioned by way of Example l-p-aminobenzoylamino 8-naphthol-3,6- or -4,6-disulfonic acid, 1 (4methoxy-3'-aminobenzoylamino) 8 naphner and coupled in acetic acid solution with 27,5

thol-3,6- or -4',6-disulfonic or -4-monosulfonic acid, 1 (4' methyl-3'-aminobenzoylamino) 3,6 disulfonic acid and 4-chloro-3'-aminobenzoylamino-4,6-difulfonic acid.

My new dyestuffs are in form of their alkali metal salts generally dark watersoluble powders, dyeing the cellulosic fibre generally bluish shades 15 which by diazotizing and developing with a yellow component, such as methylketol, acetoacetic acid arylamides, pyrazolones and the like, yield green shades of excellent clearness and good fastness properties.

The invention is illustrated by the following examples, without being limited thereto:

Example 1.-19,5 grams of the sodium salt of p-sulfanilic acid are diazotized in the usual mangrams of the sodium salt of l-amino-Z-ethoxynaphthalene-G-sulfonic acid. The monoazodyestuff formed is sucked ofi, dissolved in water to form a neutral solution, then 7 grams of sodium nitrite are added, the solution is cooled down to zero and c.c.s. of hydrochloric acid of 19 B. are quickly added. When the diazotization is complete, the solution is passed into a mixture of 500 cos. of water, 500 0.0.5. of pyridine, 300 grams of ice and containing dissolved 48,2 grams of 1-p-aminobenzoy1amino-8-hydroxynaphtha lene-3,6-sodium-disulfonate, while thoroughly stirring. The coupling is complete immediately the dyestuff is isolated by neutralization with hydrochloric acid. By redissolving from hot water and salting out it can be purified. In its free state it has probably the following formula:

no NH-O 0-QNH:

gndq HOSS H01;

The sodium salt of the dyestufi is a dark powder, soluble in water with a blue coloration and in concentrated sulfuric acid with a greenishblack coloration. It dyes cotton blue shades,

which by diazotization and developing with a yellow component yield clear green shades of SOIH 1, there is obtained a dyestufi having in its free state the following iormula:

O CzH HO NH-C O NH] good fastness and excellent discharge properties.

Dyestufis of similar properties are obtained when substituting in the above described dyestuff the p-sulfanilic acid by l-naphthylamine- 4-sulf0nic acid, anthranilic acid and dehydrothiotoluidine sulfonic acid and/or by substituting the 1-amino-2-ethoxynaphthalene-6-sulfonic acid by the corresponding methylether or the corresponding 'Y-sulfonic acid.

Example 2.--By diazotizing 24 grams of the sodium salt of 3-chloro-2-toluidine-5-sulfonic acid, coupling with 27,5 grams of the sodium salt of 1-amino-2-ethoxynaphthalene-6-sulfonic acid, further diazotizing and coupling with l-p-aminobenzoylamino 8 napthol 3,6 disulfonic acid, analogously to the process described in Example 1, there is obtained a dyestufi having in its free state the following formula:

HOIS

The sodium salt of the dyestufl. is a dark powder, soluble in water with a greenish-blue and in concentrated sulfuric acid with an olive coloration. It dyes cotton greenish-blue shades, which by diazotization and developing with a yellow component yield clear green shades of good Iastness and excellent discharge properties.

The sodium salt of the dyestuff is a dark powder, soluble in water with a bluish-green and in concentrated sulfuric acid with a blackish-olive coloration. It dyes cotton bluish-green shades, which by diazotization and development with a yellow component yield clear green shades 01. good fastness and excellent discharge properties.

I claim:

1. The new azodyestuils of the general forwherein R stands for a radical of the benzene or naphthalene series containing a sulfonic or carboxylic acid group, one X stands for hydrogen and the other X stands for hydrogen or a sulfonic acid group, R stands for alkyl, n stands for one of the numbers one and two, and wherein the benzene nucleus R may be further substituted by substituents selected from the group consisting of halogen, alkyl and alkoxy, being in form of their alkali metal salts dark, water soluble powders, dyeing the cellulosic fibre generally bluish shades, which by diazotizing and developing with a yellow component yield green shades of excellent clearness and good fastness properties.

2. The new azodyestuifs of the general formula:

HO NH-C O R CX l l X X wherein R stands for a benzene or napthalene nucleus which is substituted by substituents selected from the group consisting of the sulfonic acid group and the carboxylic acid group and which may be further substituted by substituents selected from the group consisting of alkyl, alkoxy and nitro, one X stands for hydrogen and the other X stands for hydrogen or a sulfonic acid group, R stands for alkyl, 11 stands for one of the numbers one and two, and wherein the benzene nucleus R may be further substituted by substituents selected from the group consisting of halogen, alkyl and alkoxy, being in form of their alkali metal salts dark, watersoluble powders, dyeing the cellulosic fibre generally bluish shades,

ona

which by diazotizing and developing with a yellow component yield green shades of excellent clearness and good fastness properties.

3. The new azodyestuffs of the general formula:

developing with a yellow component yield green shades of excellent clearness and good fastness properties.

4. The new azodyestufi of the folowing formula:

0 cm, no NH-C GONE:

son:

being in form of its alkali metal salts a dark powder, soluble in water with a greenish-blue and in concentrated sulfuric acid with an olive coloration and dyeing cotton greenish-blue shades, which by diazotization and developing with a yellow component yield clear green shades of good fastness and excellent discharge properties.

5. The azodyestufi of the following formula:

0 Calls HO NH-G O NH:

wherein R stands for a benzene or napthalene nucleus which is substituted by substituents selected from the group consisting of the sulfonic acid group and the carboxylic acid group and which may be further substituted by substituents selected from the group consisting of alkyl, alkoxy and nitro, one 'X stands for hydrogen and the other X stands for hydrogen or a sulfonic acid S OaH group, R stands for a methyl or ethyl group, n stands for one of the numbers one and two, and wherein the benzene nucleus R" may be further substituted by substituents selected from the group consisting of halogen, alkyl and alkoxy, beingin form of their alkali metal salts dark, watersoluble powders, dyeing the cellulosic fibre generally bluish shades, which by diazotizing and I O 00 83th:

SOaH

being in form of its alkali metal salts a dark powder, soluble in water with a bluish-green and in concentrated sulfuric acid with a blackisholive coloration, and dyeing cotton bluish-green shades, which by diazotization and development with a yellow component yield clear green shades of good fastness and excellent discharge properties.

JOSE STEPHEN PETRUS-BLUMBERGER. 

